The effect of weathering on per- and polyfluoroalkyl substances (PFASs) from durable water repellent (DWR) clothing

Journal Pre-proof The effect of weathering on per- and polyfluoroalkyl substances (PFASs) from durable water repellent (DWR) clothing Ike van der Veen, Anne-Charlotte Hanning, Ann Stare, Pim E.G. Leonards, Jacob de Boer, Jana M. Weiss PII:

S0045-6535(20)30293-9

DOI:

https://doi.org/10.1016/j.chemosphere.2020.126100

Reference:

CHEM 126100

To appear in:

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Received Date: 14 October 2019 Revised Date:

31 January 2020

Accepted Date: 2 February 2020

Please cite this article as: van der Veen, I., Hanning, A.-C., Stare, A., Leonards, P.E.G., de Boer, J., Weiss, J.M., The effect of weathering on per- and polyfluoroalkyl substances (PFASs) from durable water repellent (DWR) clothing, Chemosphere (2020), doi: https://doi.org/10.1016/ j.chemosphere.2020.126100. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2020 Published by Elsevier Ltd.

Sample CRediT author statement Ike van der Veen: Developing and validating extraction and analyses of all analysed PFASs in textiles. Performing all extractions, analyses and calculations. Perfoming all data analyses. Writing the manuscript. Anne-Charlotte Hanning: Collecting the outdoor clothing, performing and supervising the weahering Ann Stare: Performing the weathering Pim E.G. Leonards: Supervising, Reviewing writing and Editing Jacob de Boer: Supervising, Reviewing writing and Editing Jana M. Weiss: Supervising, Reviewing writing and Editing

PFCAs

DWR FTMACs PFSAs

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The effect of weathering on per- and polyfluoroalkyl substances

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(PFASs) from durable water repellent (DWR) clothing

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Ike van der Veen*a, Anne-Charlotte Hanningb, Ann Stare b, Pim E.G. Leonardsa, Jacob de

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Boera, Jana M. Weissc

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a

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Department of Environment and Health, Vrije Universiteit, De Boelelaan 1085, 1081 HV, Amsterdam, The Netherlands

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b

RISE IVF AB, Argongatan 30, SE-431 53, Mölndal, Sweden

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c

Department of Environmental Science, Stockholm University, Svante Arrheniusv. 8, SE-11418 Stockholm,

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Sweden

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*Corresponding author: E-mail address: [email protected]. Phone number: 0031 (0)20 59 82793

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Declarations of interest: none

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Abstract

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To assess the effects of weathering on per- and polyfluoroalkyl substances (PFASs) from durable water repellent

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(DWR) clothing, thirteen commercial textile samples were exposed to elevated ultra violet (UV) radiation,

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humidity, and temperature in an aging device for 300 h, which mimics the lifespan of outdoor clothing. Before

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and after aging, the textile samples were extracted and analysed for the ionic PFASs (perfluoroalkyl acids

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(PFAAs), perfluorooctane sulfonamide (FOSA)) and volatile PFASs (fluorotelomer alcohols (FTOHs), acrylates

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(FTACs) and methacrylates (FTMACs)). Results showed that weathering can have an effect on PFASs used in

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DWR of outdoor clothing, both on the PFAS profile and on the measured concentrations. In most weathered

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samples the PFAA concentrations increased by 5- to more than 100-fold, while PFAAs not detected in the

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original textiles were detected in the weathered samples. DWR chemistries are based on side-chain fluorinated

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polymers. A possible explanation for the increase in concentration of the PFAAs is hydrolysis of the

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fluorotelomer based polymers (FTPs), or degradation of the FTOHs, which are used in the manufacturing of the

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FTPs. The concentrations of volatile PFASs also increased, by a factor up to 20. Suggested explanations are the

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degradation of the DWR polymers, making non-extractable fluorines extractable, or the transformation or

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degradation of unknown precursors. Further research is needed to unravel the details of these processes and to

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determine the transformation routes. This study shows that setting maximum tolerance limits only for a few

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individual PFASs is not sufficient to control these harmful substances in outdoor clothing.

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Keywords

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Per- and polyfluoroalkyl substances; outdoor clothing; textile; weathering; aging; durable water repellency

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1 Introduction

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Per- and polyfluoroalkyl substances (PFASs) are a class of man-made chemicals, which do not occur in nature.

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Nowadays, they are ubiquitously present in water, soil, air and biota, and also in human blood and mother’s

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milk (Yoo et al., 2008; Butt et al., 2010; Kwadijk et al., 2010; Rotander et al., 2012; Cariou et al., 2015; Mørck

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et al., 2015; Olsen et al., 2017). PFASs are used in a wide range of consumer products such as in firefighting

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foams, cooking pans, carpets and food wrapping paper. Among the multitude of applications, PFASs are also

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used in textiles for outdoor clothing (Buck et al., 2011) in order to obtain the desired durable water repellence

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(DWR). DWR chemistries are based on side-chain fluorinated polymers(Holmquist et al., 2016). PFASs are

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divided into short-chain, and long-chain PFASs by their alkyl chain length (CnF2n+1), with n ≥ 6 for long-chain

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perfluoroalkane sulfonic acids (PFSAs), and n ≥ 7 for long-chain perfluoroalkyl carboxylic acids (PFCAs)

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(Buck et al., 2011; Holmquist et al., 2016). Since it was revealed that some of the PFASs are very persistent in

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the environment(US-EPA, 2011), bioaccumulative (de Vos et al., 2008; Stahl et al., 2011) and (eco)toxic

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(Hekster et al., 2003; Olsen et al., 2007; Lopez-Espinosa et al., 2011; Corsini et al., 2012; Liu et al., 2014), the

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use and production of some PFASs was regulated. In 2006 the European Commission regulated the level of

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perfluorooctane sulfonate (PFOS) in consumer products (Regulation Directive 2006/122/EC) (EU, 2006). In

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June 2017, perfluorooctanoic acid (PFOA) and PFOA-related substances, including salts and polymer

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containing -C8F17 as structural element, have been added to REACH annex XVII restricted substances list (entry

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68) by the European Commission (EU, 2017). Some of the longer chain PFCAs (C8, C11–C14) were included in

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the Candidate List of Substances of Very High Concern (SVHC) under REACH (ECHA), and recently also

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perfluorohexane sulfonate (PFHxS) was added to that list (ECHA, 2017). In 2009 PFOS and in 2017 PFOA and

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its salts have been listed in Annex B of the Stockholm Convention (decisions SC-4/17 and SC-9/12), which

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describes the restriction of production and use of the compounds (UNEP; UNEP, 19–23 October 2015; EU,

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2017). Finally, in 2019 the conference of the parties (COP) decided to list PFOA and its salts in Annex A

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(decision UNEP/POPS/COP.9/CRP.14) (IISD; EU, 24.4.2019 ). PFHxS is currently proposed to be listed as a

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POP under the Stockholm Convention(UNEP, 17–20 October 2017). Nowadays, the textile industry is phasing-

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out the long-chained PFASs (Holmquist et al., 2016) and is replacing those compounds with alternative

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chemicals that also deliver the desired DWR effect. Those alternative chemicals can be divided in three main

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groups: fluorocarbon-based, silicon-based and hydrocarbon-based polymers (Schultz et al., 2003). Hill et al.

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(Hill et al., 2017) assessed the repellent performance of some hydrocarbon-based DWRs in comparison with the

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long-chained PFAS DWR, and within the SUPFES (Substitution in Practice of Prioritized Fluorinated

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Chemicals to Eliminate Diffuse Sources) project alternative DWRs from all three main groups were assessed in

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comparison with PFASs with regard to their functionality and their impact on the environment (SUPFES, 2013-

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2016; Schellenberger, 2019).

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Some studies have been performed before on the concentrations of PFASs in textiles (KEMI, 2006; SFT, 2006;

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SSNC, 2006; Guo et al., 2009; Herzke et al., 2012; Santen and Kallee, 2012; Brigden et al., 2013; Kallee and

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Santen, 2013; Brigden et al., 2014; Greenpeace, 2014; Vestergren et al., 2015; Gremmel et al., 2016; Robel et

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al., 2017). Gremmel et al. analysed 16 outdoor jackets for the concentrations of 23 PFASs (Gremmel et al.,

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2016). All jackets contained at least one of the PFASs. Brigden et al. (Brigden et al., 2013) reported the

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detection of PFASs in 15 articles including seven waterproof garments, and Robel et al.(Robel et al., 2017)

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reported the analyses of nine textiles, which included seven garment samples. Not only PFASs in outdoor

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clothing have been analysed, but also the leaching of PFASs from the garments during washing was

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investigated. Knepper et al. (Knepper et al., 2014) reported PFAS concentrations in washing water after washing

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of outdoor jackets. Until now, no studies have been performed on the effect of different weather conditions on

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PFASs in textiles. As part of the SUPFES project, the present study was conducted with an aim to assess the

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influence of weathering on PFASs in DWR-treated outdoor clothing. The hypothesis was that PFASs used in the

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DWR-treated outdoor clothing is a relevant source of environmental pollution and human exposure due to

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emission of PFASs during usage.

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2 Material and methods

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2.1 Chemicals and reagents

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All analysed PFASs and isotope-labeled perfluoroalkyl acids (PFAAs), are shown in the Tables S1 (ionic

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PFASs) and S2 (volatile PFASs) of the Supplementary Material (SM) according to the terminology of Buck et

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al. (Buck et al., 2011). Three mixtures containing 50 µg mL-1 of FTOHs (4:2, 6:2, 8:2, and 10:2), FTACs (6:2,

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8:2, 10:2), and FTMACs (6:2, 8:2, 10:2) in methanol, and individual solutions of 50 µg mL-1 of the isotope

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labeled D2-6:2 FTOH, D3-6:2 FTAC and D5-6:2 FTMAC in methanol, were purchased from Chiron AS

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(Trondheim, Norway). The purities of those mixtures were >98%, and the isotope purity of D2-6:2 FTOH, D3-

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6:2 FTAC and D5-6:2 FTMAC was >99%. All other PFASs (50 µg mL-1 in methanol, purity of > 98%.) were

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purchased from Wellington Laboratories (Guelph, ON, Canada). The isotope purity of the isotope-labeled

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PFAAs was >99%, except for 18O2-PFHxS (>94%). HPLC grade methanol (J.T. Baker, 8402), and acetone (J.T.

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Baker, 9254) were obtained from Boom (Meppel, The Netherlands). Ethylacetate (HPLC, 054006) was

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purchased from Biosolve Chimie (Dieuze, France). Acetonitrile (Chromasolve, 34851), ammonium formate

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(Bio ultra, 09735), and SupelcleanTM Envi-carbTM (Supelco, 957210-U) were purchased from Sigma Aldrich

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(Zwijndrecht, The Netherlands). A Milli-Q system from Millipore (Watford, UK) was used to obtain ultrapure

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water. Glass fiber filters (GF/F, pore size 0.42 µm), purchased from Whatman (Maidstone, UK), were used for

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filtering of the mobile phase.

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2.2 Textile samples

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Textile samples originating from outdoor clothing (one pair of outdoor trousers, seven jackets, four fabrics for

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outdoor clothes, and one outdoor overall, Table 1), were provided by six different suppliers from the outdoor

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textile industry in Sweden to SWEREA IVF (Mölndal, Sweden). Two pieces were cut out of each fabric. One of

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the pieces (9 cm x 12 cm) was exposed in an ATLAS weather-Ometer Ci 3000 to elevated UV radiation,

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humidity, and temperature for 300 h (Table 2), which can be compared to the lifespan of the outdoor

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clothing(Lv et al., 2009). Both pieces of textile, aged and not aged, were analysed for ionic PFASs and volatile

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PFASs content. Until analyses, all pieces of textile were stored at room temperature in the dark.

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Table 1. Details of outdoor clothing samples.

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Sample No. 1 2 3 4 5 6 7 8 9 10 11 12 13 nr *

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Table 2. Conditions of ATLAS weather-Ometer Ci 3000 for a weathering experiment (total duration 300 h)*.

Sample type

Sample color

Outdoor trousers Fabric for jacket Fabric for jacket Men’s jacket Men’s jacket Fabric for outdoor clothes Children’s jacket Jacket (parka) Fabric for outdoor clothes Fabric for outdoor clothes Fabric for outdoor clothes Fabric for outdoor clothes Fabric for outdoor clothes – not reported – information given by supplier

Black Anthracite Olive Brown Yellow Yellow Brown Olive Yellow Green Yellow Light blue Bright blue

Method

A1 (ISO 4892-2)

116 117 118 119 120

* **

Exposure cycles

Broadband (300-400 nm) W m-2 60 ± 2

Year of manufacturing* nr nr nr 2013 2013 2012 2012/2013 nr nr nr nr nr nr

Narrowband (340 nm) W m-2⋅nm 0.51 ± 0.02

Fabric* 100% recycled polyester 80% polyester, 20% cotton 100% polyamide 100% cotton 100% polyester 65% cotton, 35% polyester 100% polyamide nr 100% polyester nr nr nr 100% polyester

Black standard temperature** (˚C) 65 ± 3

Chamber temperature (˚C) 38 ± 3

Humidity (%)

102 min dry 50 ± 10 18 min water spray Conditions as described in ISO 4892-2 method A1(Alzaga et al., 2005), and ISO 105-B10 Exposure method A(Lv et al., 2009) Reference temperature on a black metal plate in the ATLAS weather-Ometer Ci 3000, which characterizes the temperature on the sample surface (Tönning Kathe et al., 2009)

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2.3 Extraction procedure

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2.3.1

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Circular pieces with a diameter of 35.3 mm (equals 9.79 cm2) were taken from the aged and unaged outdoor

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clothes samples by a bore (Cordia Matic, 270 rpm) for analysis of ionic PFASs. Extraction was performed

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according to the method of Van der Veen et al. (Van der Veen et al., 2016), which was developed and validated

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after comprehensive testing of different solvents and exhaustive extraction. In short, dust particles were rinsed

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from the textile pieces by adding 5 mL water to the test tube and taking the textile piece out immediately

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afterwards. After adding 150 µL isotope labeled internal standard solution (conc. 100 ng mL-1) (Table S1), the

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samples were left to equilibrate for one night. Ionic PFASs were extracted with two times shaking the textile

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pieces in 5 mL methanol for 30 minutes on a shaking device. After concentration until dryness by a gentle

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stream of nitrogen at 40 C, the extracts were reconstituted in 200 µL methanol: water (1:1, v/v).

Ionic PFASs

◦

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2.3.2 Volatile PFASs

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Both pieces of textile, aged and not aged, were extracted and analysed for volatile PFASs content in the same

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series. Because of the limited amount of textile available for the analyses of volatile PFASs, squares of

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approximately 20 cm2 were cut with a pair of scissors from each aged and unaged outdoor clothes sample,

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instead of cutting by a bore.

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To enhance extraction performance, each piece of textile was cut into eight smaller pieces, which were all

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weighed together into a 15 mL polypropylene (pp) tube. The samples were fortified with 50 µL of an IS solution

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(mixture of 800 ng mL-1 D2-6:2 FTOH, 800 ng mL-1 D3-6:2 FTAC and 200 ng mL-1 D5-6:2 FTMAC in

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ethylacetate, which equals concentrations of 20, 20 and 5 µg m-2, respectively), added directly onto the samples

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and left to equilibrate for one night (IS recoveries are given in Table S7). Volatile PFASs were extracted from

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the samples by liquid solid extraction (LSE) with 2 times 5 mL ethylacetate. Extraction was performed by

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shaking on a shaking device (Edmund Bühler GmbH, Hechingen, Germany) for 30 min. The extracts were

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concentrated to a volume of approximately 1 mL by a gentle stream of nitrogen at 20°C. The extracts were

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purified by adding 100 mg Envi-carbTM followed by mixing on a Vortex and centrifugation (10 min, 3000 rpm).

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The final extracts were concentrated to a volume of 100 µL by a gentle stream of nitrogen at 20°C.

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2.4 Instrumental analysis and quantification

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2.4.1 Ionic PFASs

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The extracts were analysed for ionic PFASs by electrospray negative ionization LC-MS/MS as previously

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described by Van der Veen et al.(Van der Veen et al., 2016). Instrumental settings are reported in Table S3.

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2.4.2 Volatile PFASs

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Separation and detection of volatile PFASs was carried out by GC/EI-MS (Gas chromatography/ Electron

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impact-Mass spectrometry) on an Agilent 6890 series GC coupled to a 5973 Network MS (Agilent

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Technologies, Amstelveen, The Netherlands) equipped with a PTV injector without liner. Separation was

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performed on a HP-INNOWax column (30 m x 0.25 mm i.d. x 0.25 µm; Agilent Technologies, Amstelveen,

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The Netherlands) using the following GC temperature programming: 50°C (held 1 min), ramped at 3°C min-1 to

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130°C (held 10 min), ramped at 20°C min-1 to 225°C (held 11 min). An injector temperature program was used,

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with an initial temperature of 50°C (held for 0.1 min), ramped at 5°C sec-1 to 150°C (held 10 min), ramped at

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3.3°C sec-1 to 220°C (held 1 min). Injection volume was 1 µL in pulsed splitless mode. Helium was employed

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as the carrier gas. Quantification was performed against three individual calibration curves (FTOHs, FTACs and

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FTMAC) consisting out of six calibration solutions (5, 10, 25, 50, 100, 500 ng mL-1) for FTACs and FTMACs

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and eight solution for FTOHs (5, 10, 25, 50, 100, 500, 2500, 5000 ng mL-1) in ethylacetate, and against the

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isotope-labeled ISs D2-6:2 FTOH, D3-6:2 FTAC and D5-6:2 FTMAC. Instrumental settings are reported in Table

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S4. For quantification MSD Chemstation software (E.02.00.493) of Agilent Technologies (Amstelveen, The

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Netherlands) was used with quadratic curves.

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2.5 Quality control

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2.5.1 Validation of the extraction and analyses method for volatile PFASs

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The extraction and analysis method for the volatile PFASs was validated by assessment of the repeatability and

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the recovery. All textile samples of the repeatability and recovery assessment were extracted and analysed in the

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same series. For both assessments the same calibration curves were used. To assess the repeatability of the

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method, two textile samples were extracted in triplicate on the same day. To assess the recovery of the method,

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those textiles were fortified with volatile PFASs at two different levels (50 and 500 µg m-2) in triplicate.

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Calculations of the repeatability and the recovery are given in Chapter S3. The relative standard deviations for

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the triplicate analyses of the unfortified samples were 5-17% for PFASs. The relative standard deviations of the

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fortified textile samples were 0-28%. The recoveries were 60-130% (median 100%) for all compounds except

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10:2 FTOH (86-159%, median 98%), and 8:2 FTAC (103-146, median 132%).

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2.5.2 Carry-over and blank control

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Two textile fabrics (polyamide and polyester) without any DWR-treatment were exposed to UV radiation,

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humidity, and temperature alongside the cloth samples, to determine any possible carry-over in the aging device.

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No ionic PFASs were detected in the textiles before and after aging. Only 6:2 FTOH was present of the volatile

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PFASs before aging in both textiles (9.3 and 13 µg m-2). After aging the concentration of 6:2 FTOH increased

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with an average of 5 µg m-2, and small amounts of 8:2 FTOH (4 µg m-2), 10:2 FTOH (4 µg m-2) and 6:2

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FTMAC (2 µg m-2) were detected, which were subtracted from the final results. Only results higher than three

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times the amount detected in the blank textiles were reported.

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Procedure solvent blanks were analysed alongside the samples and subtracted from the final results.

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limits of detection (LODs) of the ionic PFASs were between 0.02 and 0.1 µg m-2, and LODs of the volatile

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PFAS were 0.3 µg m-2. The limit of quantification (LOQ) was calculated as 3.3 times the LOD. (Chapter S3).

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2.5.3 Homogeneity testing of PFAAs in textiles from commercial outdoor clothing

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Homogeneity tests of PFAAs have been performed on pieces of textile originating from four fabrics of

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commercial outdoor clothing, which is described in Chapter S4 of the supplementary material. Results showed

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that the homogeneity differs per fabric, but can also differ per piece of the same material, which is shown for

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PFOA in Figure 1.

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Figure 1 Results of homogeneity testing of mean PFOA concentration (+/- 1 sd) (µg m-2) in four fabrics (Fabric No 1 – 4) of commercial outdoor clothing. (‘n’ represents the number of samples analysed per piece of fabric).

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3 Results and discussion

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3.1 Concentrations before weathering

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As expected, the fabrics contained a wide range of levels of PFASs with different congener profiles depending

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on the DWR layer. Tables S5 and S6 show the concentrations of ionic PFASs and volatile PFASs in the original

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samples. Volatile PFASs were present in higher concentrations (median 4.8 µg m-2, max. 350 µg m-2) than ionic

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PFASs (median 0.85 µg m-2, max. 45 µg m-2).

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3.1.1 Ionic PFASs

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In 77% of the samples at least one of the ionic PFASs was detected. PFHxA and PFOA were the most

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frequently detected PFAAs above limit of quantification (LOQ) (each detected in 62% of the samples).

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PFTrDA, PFHpS, FOSA, and 4:2 FTSA were not present above the LOQ in any of the samples. The highest

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concentration was 45 µg m-2 for PFBS in one of the samples. This sample also contained a high amount of

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PFBA (28 µg m-2). For all other PFAAs the concentrations in the unexposed samples ranged from < LOQ to 9.1

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µg m-2 for 8:2 FTSA. Those concentrations were in the same range as reported by Gremmel et al.(Gremmel et

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al., 2016), and of Robel et al.(Robel et al., 2017). Concentrations of individual PFAAs in 16 outdoor jackets

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reported by Gremmel et al.(Gremmel et al., 2016) ranged up to 9.24 µg m-2, except for one jacket which

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contained PFOA in a concentration of 171 µg m-2. The highest concentration of PFAA reported by Robel et

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al.(Robel et al., 2017) for seven clothing samples was 31 µg m-2 for PFHxA.

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3.1.2 Volatile PFASs

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Since volatile PFASs can easily evaporate, concentrations detected in the fabrics in our study might be

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underestimating the real concentrations present in the fabrics. However, the detected concentrations are in line

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with the studies of Gremmel et al. (Gremmel et al., 2016), and of Robel et al.(Robel et al., 2017). The highest

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concentration quantified for volatile PFASs in our study was 350 µg m-2 for 6:2 FTOH. Gremmel et

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al.(Gremmel et al., 2016) reported concentrations up to 516 µg m-2 for individual FTOHs. In all of their samples,

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except one, 8:2 FTOH was detected, which corresponds to the results from our study. It is remarkable though,

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that in our study all samples except one contained 6:2 FTOH, while in the study of Gremmel et al. (Gremmel et

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al., 2016) 6:2 FTOH was only quantifiable in two samples. In the study of Robel et al.(Robel et al., 2017) 6:2

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FTOH was detected in four of seven samples. In one of those samples an extremely high concentration (14000

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µg m-2) was found. In our study 10:2 FTOH was found in eleven out of thirteen samples and 6:2 FTMAC in

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nine samples. 8:2 FTMAC and 10:2 FTMAC were not detected at all. 4:2 FTOH was not detected in any of the

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samples. Due to the high costs of isotope-labeled standards only D2-6:2 FTOH was used as internal standard for

232

the quantification of 4:2 FTOH, which might have been insufficient to compensate for eventual losses during

233

extraction and analyses due to the volatility of the short-chain 4:2 FTOH.

234 235

3.2 Effects of weathering

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3.2.1 Ionic PFASs

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Weathering increased the concentrations of all ionic PFASs in most samples, by 5-fold to more than 100-fold.

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Three samples did not contain any ionic PFASs before aging. In one of those samples, no ionic PFASs were

239

found after aging, while in another sample after aging two PFAAs (PFHpA, 0.16 µg m-2; PFNA 0.13 µg m-2)

240

appeared. In the third sample six different PFAAs appeared with concentrations of 0.1 µg m-2 (PFOA) – 7.1 µg

241

m-2 (PFBA). Tables S5 and S6 show all extractable concentrations of ionic PFASs and volatile PFASs in the

242

samples before and after aging, and Figure 2 shows four selected samples to illustrate different results. As can

243

be observed, the concentrations of all PFCAs in samples 5 and 6 increased, and the odd-chain length PFASs

244

PFUnDA and PFTrDA appeared. In sample 9 the most abundant ionic PFASs were the compounds with a C4

11 245

chain length, PFBA and PFBS, which increased 5 and 8 times, respectively. Sample 13 did not contain any ionic

246

PFASs before aging, while 6 PFASs were detected in the samples after aging. In Figure S1 the results of all the

247

samples are shown.

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248 249 250 251 252

Figure 2 PFASs concentrations quantified in four textile samples of outdoor clothing (sample 5, 6, 9 and 13). Concentrations of ionic PFASs (■before; ■after) in µg m-2 on the left y-axis. Concentrations of volatile PFASs ( before; after) in µg m-2 on the right y-axis. The PFAS concentrations in the other textile samples are given in Figure S1 and Table S5, and S6.

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Robel et al. (Robel et al., 2017) performed a study on the mass balance of PFASs. They analysed 77 individual

254

PFASs in nine textiles and eight papers, and analysed the total amount of organic fluor by particle induced

255

gamma ray emission (PIGE) spectroscopy. After extraction the papers and textiles still contained 64 ± 28% to

256

110 ± 30% of the original concentration, expressed in nmol F.cm-2. The high non-extractable organic fluor

257

(NEOF) fraction was also described by Koch et al. (Koch et al., 2019), and by Schultes (Schultes, 2019). Within

258

our study the amount of total organic fluor was not determined, but it is expected that the textiles before aging

259

also contained NEOF. The increase of PFAAs as an effect of the exposure to weather conditions might be

260

explained by the NEOF, which could have become partially extractable due to weather conditions.

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Another explanation for the increase in PFAAs as an effect of the exposure to weather conditions, might be the

262

degradation and transformation of the precursors FTOHs, FTACs, and FTMAC, which are used for the

263

formation of the DWR polymers. The degradation and transformation of FTOHs into PFCAs has been described

264

multiple times(Buck et al., 2011), including aerobic biodegradation(Dinglasan et al., 2004; Wang et al., 2005;

265

Liu et al., 2007; Wang et al., 2009; Kim et al., 2014), anaerobic biodegradation(Li et al., 2018), metabolic

266

transformation(Russell et al., 2015), and atmospheric degradation(Ellis et al., 2004; Wallington et al., 2006).

267

Photodegradation might be the degradation and transformation route when precursors are exposed to weather

268

conditions. Taniyasu et al. (Taniyasu et al., 2013) tested the influence of solar irradiation on 21 PFASs in test

269

solutions in a field study, and in a laboratory study in which the solutions were irradiated in a UV chamber.

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Although results of their study indicated photodegradation of PFOA, PFNA, PFDA, PFOS, PFDS, 4:2 FTOH,

271

6:2 FTOH, and 8:2 FTOH, the conclusions of their study are being questioned, because of the lack of essential

272

experimental details, the lack of plausible transformation mechanisms, and the inconsistency of results (Wang et

273

al., 2015). However, the photodegradation of PFAAs in aqueous solutions under special conditions, with PFAAs

274

decomposing slowly to form F−, CO2, and shorter-chain PFCAs, has been described earlier by Hori et al. (Hori

275

et al., 2004; Hori et al., 2007). Also Kongpran et al. (Kongpran et al., 2014) performed experiments that showed

276

photodegradation of FTOHs into PFCAs. Since PFCAs in their study were formed at a very slow rate, the

277

authors concluded that 8:2 FTOH did not degrade to PFCAs directly, but first to some intermediate products

278

(Kongpran et al., 2014).

279

Degradation of the FTOHs, or (part of) the NEOF becoming extractable might not only explain the increase in

280

concentrations of the ionic PFASs in our study, but also the formation of odd-chain length PFASs in some of the

281

samples, which were not present in the original textiles.

282

14 283

3.2.2 Volatile PFASs

284

If the increase in concentrations of ionic PFASs would only be the result of the transformation of the volatile

285

PFASs into ionic PFASs, it could be expected that the concentrations of volatile PFASs would decrease when

286

exposed to weather conditions. In contrast with this expectation, the volatile PFASs show an increase in

287

concentrations after aging, by a factor up to 20. No 4:2 FTOH, 8:2 FTMAC and 10:2 FTMAC were formed,

288

while the concentration of 6:2 FTOH increased in all samples except in sample 5 (Figure 2, Table S6). It is

289

possible that sample 5 did not contain any precursors of 6:2 FTOH. However, since in all samples the

290

concentration of 6:2 FTOH increased by a factor of 2.4-16, the decrease in sample 5 might possibly be due to

291

inhomogeneity of the textile (section 0). Confirmation of this hypothesis was not possible since there was not

292

enough material to perform homogeneity tests on the commercial textile samples, which were used for the aging

293

experiments.

294

Although concentrations of volatile PFASs could be underestimated due to off-gassing during storage (section

295

3.1.2), the differences between the concentrations before and after aging could not be explained by this, since all

296

samples were stored at the same temperature, and analysed in the same series.

297

In the study of Robel et al. (Robel et al., 2017) where 77 individual PFASs were quantified in paper and

298

textiles, the analyses of the total amount of organic fluor by PIGE spectroscopy showed that only 0-2.2% of the

299

total amount of organic fluor was explained by the analysed volatile PFASs, and only 0-0.41% by the analysed

300

ionic PFASs. The remaining organic fluor in the study of Robel et al. (Robel et al., 2017) might be in the

301

fluorotelomer based polymers (FTPs). Since nowadays more than 2,000 different PFASs are present on the

302

market (KEMI, 2015), part of the remaining organic fluor might also be non-polymeric PFASs that were not

303

included in the analysis. In our study, only 29 individual PFASs were analysed. It is likely that more non-

304

polymeric PFASs were present in the unexposed samples. Possibly, some of the PFASs that were not analysed

305

in this study could have been degraded or transformed into the volatile PFASs, analysed in our study. It cannot

306

be ruled out that more volatile PFASs were formed and emitted to the air, or to the spray water. Further research

307

with e.g. total organic fluor analyses, and total oxidizable precursor (TOP) assays (Zhang et al., 2019) is needed

308

to complete the balance on PFASs present before and after weathering.

309

Another explanation for the increase in the concentrations of volatile PFASs as an effect of the exposure to

310

weather conditions might come from the FTPs. DWR chemistries of outdoor clothing are not based on the

311

individual volatile PFASs, like alcohols and acrylates, but are based on side-chain fluorinated polymers

15 312

(Holmquist et al., 2016). FTPs can degrade to FTOHs and FTACs in the environment (Li et al., 2017). This was

313

also demonstrated by Washington et al. (Washington et al., 2015). They reported degradation of two commercial

314

acrylate-linked FTPs in soil and water and monitored 71 analytes. Fifty of those were detected in the final

315

samples, which made the authors conclude that commercial FTPs can degrade under environmental conditions

316

at levels that are detectable. Additional experiments performed by Washington et al. (Washington et al., 2015)

317

suggested hydrolysis of the ester linkage of the FTP as a degradation mechanism, and a follow-up study showed

318

not only an increase of FTOH concentrations, but also of PFCAs (Washington and Jenkins, 2015). The half-

319

lives reported by Washington and Jenkins were 55 years for 8:2 FTOH and 89 years for 10:2 FTOH at 25°C

320

(Washington and Jenkins, 2015). Considering the black standard temperature (Table 2) during aging in our

321

study was 65°C, it is expected that the half-lives in our study would be much shorter (Tebes-Stevens et al.,

322

2017). Based on the studies of Li et al.(Li et al., 2017), Washington et al. (Washington et al., 2015), and

323

Washington and Jenskins (Washington and Jenkins, 2015) not only the increase in the concentrations of volatile

324

PFASs in our study may be explained by the degradation of the DWR polymers themselves, or by hydrolysis of

325

the FTPs, but also the increase of ionic PFASs could be explained by hydrolysis of the FTPs.

326

Finally, the increase of the volatile PFAS concentrations might also be explained by the NEOF becoming

327

extractable under influence of weather conditions, as described in section 3.2.1.

328

An overview of potential degradation/transformation pathways of PFASs used in the DWR layer of textiles is

329

shown in Figure 3. More research is needed to reveal or confirm the processes which are responsible for the

330

increase in concentration of the analysed PFASs.

331 332

Figure 3

Potential degradation pathways of weathering of PFASs used in the DWR layer of textiles.

16 333

3.2.3 Implications of weathering

334

For PFOS and PFOA a content limit is set by the European Commission for products like textiles for outdoor

335

clothing. According to the restriction of PFOS by the European commission in 2006 (EU, 2006), its

336

concentration in coated materials should be lower than 1 µg m-2. One of the textiles of our study (Sample No.2)

337

exceeded this limit before weathering, but after aging PFOS was not detected anymore. The EU regulation for

338

PFOA (EU, 2017) states that, starting 4 July 2023, PFOA and PFOA-related substances shall not be used or

339

placed on the market in textiles used for protective clothing in a concentration equal to or above 25 µg kg-1

340

(ChemsafetyPRO, 2017). The original textile products used in this study all fulfilled this criterion for PFOA, but

341

after aging two of the tested fabrics exceeded this limit, with PFOA concentrations of 47 and 170 µg kg-1. This

342

means that setting a limit only for PFOA and related substances may not be sufficient to ensure safety. Instead

343

of regulating only PFOA and related substances, all possible precursors of PFOA, including the FTP, should be

344

taken into account when setting criteria.

345

The leaching of PFASs out of textiles, but also the increase in concentrations of PFOA and other PFASs due to

346

weather conditions might not only have an environmental impact. The use in outdoor clothing may also form a

347

direct exposure route to humans, since there is dermal contact with the textiles. Franko et al. (Franko et al.,

348

2012) showed in an in vitro study that PFOA can penetrate the human skin. As much as 24% of the applied

349

PFOA dose penetrated the complete skin, and 46% was found in the skin. In an in vivo study of mice, Franko et

350

al. (Franko et al., 2012) also showed that dermal exposure to PFOA caused an increase in PFOA levels in serum.

351

The dermal absorption of PFASs from dust was estimated by Su et al. (Su et al., 2016). They determined an

352

estimated daily intake (EDI) of 0.04-1.79 ng PFOA kg-1 bw d-1 for dermal absorption, depending on age.

353

Combining the findings in our study and the dermal uptake determined by Franko et al. (Franko et al., 2012) a

354

worst case scenario could be calculated for the dermal exposure of humans to PFOA when wearing outdoor

355

clothing.

356

In our study the highest PFOA concentration detected after aging was 54 µg m-2 (170 µg kg-1). Assuming an

357

average outdoor jacket would consist of approximately 2 m2 fabric, would result in an absolute amount of 108

358

µg PFOA in the jacket. In a worst case scenario, a person would be having direct skin contact with the entire

359

fabric of the jacket and all PFOA would be leaching out of the jacket. With 24% of the PFOA penetrating

360

through the skin (Franko et al., 2012), by wearing this outdoor jacket a person could absorb a maximum of 26

361

µg PFOA, or ca. 0.4 µg kg-1 for a person of 70 kg . This is most likely an overestimation as the concentration of

17 362

leachable PFOA was determined by extracting the material with methanol, whereas leaching of PFOA from the

363

textile in contact with the skin will be much slower.

364

The health-based safety value for human derived by the Dutch National Institute for Public Health and the

365

Environment (RIVM) is 89 ng mL-1 PFOA in serum (M. J. Zeilmaker, 2016), corresponding to 267 µg PFOA in

366

an adult with approximately 3 L serum. The maximum up-take of 26 µg PFOA from wearing the outdoor jacket

367

calculated here would correspond to 10% of this safety limit. Although it is unlikely that a human will be

368

exposed to the total amount of PFOA present in a jacket, and this worst case scenario is also based on the total

369

life time of the jacket, further research is warranted to determine the importance of this possible exposure

370

pathway of PFOA for humans.

371

372

4 Conclusion

373

Weather conditions like sunlight, high temperature, or humidity can have an effect on the congener profile and

374

concentrations of PFASs in DWR-treated outdoor clothing. In most samples the PFAA concentrations increased

375

and PFAAs not present in the original textiles were formed during weathering. A possible explanation is

376

degradation of the fluorotelomer alcohols to the PFAAs, or hydrolysis of the FTPs. The concentrations of

377

volatile PFASs also increased. Degradation of the DWR polymers is suggested as one of the possible

378

explanations for this phenomenon. Other possibilities would be non-extractable organic fluor becoming

379

extractable, or unknown precursors degrading or transforming to the analysed volatile PFASs. Further research

380

is needed to unravel the details of these processes and to determine the transformation routes. Total organic

381

fluor analyses, and TOP assays are suggested to complete the balance on PFASs present before and after

382

weathering. This study shows that setting maximum tolerance limits for a few PFASs alone is not sufficient to

383

control these harmful substances in outdoor clothing.

384 385

Acknowledgment

386

The authors are grateful to the outdoor clothing industry for supplying the outdoor clothing samples. The

387

Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning (FORMAS), Sweden is

388

acknowledged for financing this work performed within the SUPFES project (SUPFES, 2013-2016).

389

18 390

Appendix A: Supplementary material

391 392

References

393 394 395 396 397 398 399 400 401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 427 428 429 430 431 432 433 434 435 436

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Highlights • Outdoor clothing with a durable water repellent layer (DWR) are weathered • Weathering of outdoor clothing can result in an increase in PFAAs of 5-fold or more • Weathering of DWR layer results in an increase in volatile PFASs • Potential degradation pathways of the DWR are discussed • Setting maximum tolerance limits for a few PFASs alone is not sufficient

Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: